CN102351656B - Synthesis method of hydroquinone - Google Patents
Synthesis method of hydroquinone Download PDFInfo
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- CN102351656B CN102351656B CN 201110341287 CN201110341287A CN102351656B CN 102351656 B CN102351656 B CN 102351656B CN 201110341287 CN201110341287 CN 201110341287 CN 201110341287 A CN201110341287 A CN 201110341287A CN 102351656 B CN102351656 B CN 102351656B
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- resorcinol
- benzoquinone
- phenol
- hydroquinone
- reaction
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Abstract
The invention relates to a synthesis method of hydroquinone. The method is characterized by comprising the following steps: carrying out catalytic oxidation on phenol and oxygen to generate a mixture of p-benzoquinone and o-benzoquinone, wherein a catalyst is copper and sodium complex salt; distilling to remove solvent, adding water in residual materials, and separating p-benzoquinone and o-benzoquinone by distillation; reducing separated p-benzoquinone with a reducing agent to obtain hydroquinone, filtering out hydroquinone crude product and recrystallizing so as to obtain hydroquinone crystal; and concentrating a mother liquid obtained by filtering out hydroquinone or catechol crude product to obtain an ammonium sulfate fertilizer. The synthesis method has simple process, mild reaction conditions and short reaction period, and the yield of hydroquinone in the product is larger than that of catechol.
Description
Technical field
This patent relates to a kind of synthetic method of Chemicals, specifically, and the synthetic method of Resorcinol.Belong to the pharmaceutical chemistry technical field.
Background technology
Resorcinol is the important chemical product, all is used widely in industries such as chemical industry, medicine, agricultural chemicals, spices, rubber.The synthetic method of Resorcinol is as follows:
(1)
The Reppe methodBe under Ru, Rh catalyzer, temperature is that 100～300 ℃, pressure are under the condition of 100～350 MPa, and acetylene and reaction of carbon monoxide generate Resorcinol.This method technology is simple, but required catalyzer is expensive and be difficult to reclaim.
(2)
The aniline oxidation styleBe under the acidic conditions that sulfuric acid exists, with Manganse Dioxide or sodium dichromate 99 aniline be oxidized into para benzoquinone; Then with para benzoquinone under acidic conditions, with iron powder its reduction is become Resorcinol; Crystallization after filtration,, decolouring make finished product.This method maturation, be easy to control, and productive rate is higher, but generates a large amount of manganese salt, molysite and sulphur waste liquor of ammonium etc., and the rate of recovery is low, contaminate environment, raw material consumption is big, the production unit expense is higher.
(3)
Isopropyl benzene peroxidation method: at first at an acidic catalyst (phosphate diatomite or AlCl
3) exist down, carry out the synthetic diisopropylbenzene(DIPB) of Friedel-Crafts alkylated reaction by benzene and propylene, isolating para-isomeride, meta-isomer, to make its transposition be para-isomeride, the p-Diisopropylbenzene of telling is carried out peroxidation generate the di-isopropyl superoxide, and then cracking is Resorcinol and acetone in the presence of an acidic catalyst (as sulfuric acid), and product gets finished product after neutralization, extraction, centrifugation, purification, vacuum-drying.In p-Diisopropylbenzene, the Resorcinol yield is about 80 %.This method is compared with aniline process, has total cost low (hanging down 30% approximately than aniline process), pollutes advantages such as little.But because this method by product is many, and complicated component, make product separate difficulty.
(3)
The dihydroxyphenyl propane methodBe with concentrated hydrochloric acid, H with phenol and acetone
2SO
4Or ion-exchange resin catalyzed reaction generation dihydroxyphenyl propane, under the basic catalyst effect, quantitatively being cracked into phenol and isopropenyl phenol again, the latter uses hydrogen peroxide oxidation, can obtain Resorcinol and acetone.Phenol and acetone that reaction generates can be recycled.This operational path does not have the three wastes, yield height, so better economic benefit, but the equipment requirements height is not suitable for large-scale industrial production.
(4)
Phenol-hydrogen peroxide hydroxylation method: be to be raw material with phenol, under catalyst action, with hydroperoxidation, generate Resorcinol and pyrocatechol.After deviating from water, high boiling material, phenol and isolating pyrocatechol, obtain thick Resorcinol, make the Resorcinol product through dissolving, decolouring, recrystallization again.Compare with aniline process and diisopropylbenzene(DIPB) method, phenol hydroxylation method reaction process and lock out operation are simple, so energy consumption is lower, and three-waste pollution is few; In addition, the pyrocatechol of coproduction also is very important fine chemical product, is the intermediate of vanillin food grade,1000.000000ine mesh, synthetic musk and medicine, agricultural chemicals and dyestuff, also can directly be used as polymerization retarder, oxidation inhibitor etc., and this makes the extremely people favor of phenol hydroxylation technology.At present, external major company adopts this technology to produce Resorcinol more.
In the phenol hydroxylation method, the catalyzer of development and development of new is important research contents always.France Rhone-Poulence company has developed with HClO
4Be catalyzer, H
3PO
4Be the method for promotor production dihydroxy-benzene, and realized industrialization in 1973.This method adopts the hydrogen peroxide of high quality mark (70%), and phenol conversion is 5 %, and the dihydroxy-benzene selectivity is 90%, and Resorcinol in the product/pyrocatechol is than being 1.5/0.8.Owing to used perchloric acid, phosphoric acid etc. in the reaction, make the expense of equipment and materials increase, the aftertreatment technology complexity, environmental pollution is bigger.Japan Ube company is with sulfuric acid and 60% H
2SO
4Immediately the ketone peroxide that generates with methyl iso-butyl ketone (MIBK) is that catalyzer carries out the phenol hydroxylation reaction, and phenol conversion is lower than 5%, and the selectivity of dihydroxy-benzene can reach 90%, and the ratio of para-isomeride and ortho isomer is 1.5/1 in the product.Gondola Brichima company is catalyzer with the mixing salt of molysite and cobalt salt, adopts 60%H
2O
2The aqueous solution carries out hydroxylating, and the transformation efficiency of phenol is about 10%, and the selectivity of dihydroxy-benzene is about 80%, and ortho isomer is 2/3 with the ratio of para-isomeride in the product.Italy Enichem company with the TS-1 molecular sieve analog be catalyzer, with 30% H
2O
2Be oxygenant, produce Resorcinol and pyrocatechol.But this complex process consumes a large amount of molecular sieve catalysts, therefore not by large-scale promotion in the reaction.Britain Solvay Interox company makes catalyzer with heteropolyacid salts such as the molybdenum vanadium phosphorus of Keggin structure, tungsten vanadium phosphorus, molybdenum tungsten phosphorus, is solvent with the acetonitrile, has synthesized Resorcinol or pyrocatechol from the phenol highly selective, and phenol conversion is 10 %～15 %.Owing to make reaction medium with acetonitrile, the toxic of reaction process is bigger, and phenol/H
2O
2Mol ratio too low, H
2O
2Consumption too big, in addition, catalyst recovery relatively the difficulty.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of synthetic method of Resorcinol, technology is simple, the reaction conditions gentleness, reaction time is short, and the yield of Pyrogentisinic Acid's diphenol is greater than the yield of pyrocatechol in the product.
In order to realize above-mentioned goal of the invention, the present invention has adopted following technical scheme:
A kind of synthetic method of Resorcinol may further comprise the steps:
(1), phenol and Oxygen Catalytic Oxidation generate the mixture of benzoquinone and adjacent benzene diquinone, catalyzer is the composite salt of copper sodium; The reaction engineering formula is suc as formula (1):
Formula (1)
Wherein, the mol ratio of catalyzer copper sodium composite salt and phenol is between between the 1:2 to 1:20, and temperature of reaction is 60-80
oC, reaction pressure is normal pressure, and the reaction times is 2-6 hour, and solvent for use is the mixture of two or three among methyl alcohol, ethanol, propyl alcohol, butanols or the above-mentioned four kinds of alcohol.The catalyst system that adopts copper sodium composite salt to make up, reaction times, temperature of reaction have great influence to catalytic effect, at 60-80
oIn the range of reaction temperature of C, the catalyst recovery yield height, phenol catalyzed oxidation selectivity good (85 %-95 %), temperature is too high, and byproduct of reaction increases, and temperature is too low, and the reaction times increases.The mol ratio of copper sodium composite salt and phenol is between between the 1:2 to 1:20, and the oxidized selectivity of phenol is suitable, and the mol ratio of catalyzer and phenol is greater than 1:2, and selectivity improves little, and when the mol ratio of catalyzer and phenol during less than 1:20, selectivity reduces.
(2), steam solvent, add water in the residuum, through fractionation by distillation benzoquinone and adjacent benzene diquinone; The fractionation by distillation step is that the color of the aqueous solution that goes out according to steam distillation is judged progress, when the aqueous solution that distills out gradually becomes colourless by yellow, stops distillation.
(3), isolated benzoquinone obtains Resorcinol by reductive agent reduction, filter out the big and heavy crystallization of Resorcinol and obtain the Resorcinol crystal; Reductive agent and benzoquinone's mass ratio is that 2:1-1:2 is preferably 1.04:1, because under this ratio, the benzoquinone is fully reduced, and does not waste too many reductive agent; Reaction formula is seen formula (2):
Described reductive agent is in the steel-making wastewater treatment process, has extracted the residue behind the ammonium thiocyanate, and the main chemical compositions of this residue is 68.5 weight % (NH
4)
2S
2O
3(NH with 31.5 weight %
4)
2SO
4, that wherein mainly bring into play reductive action is (NH
4)
2S
2O
3The reductive agent consumption is crossed in the ammonium sulfate that generates at most and is contained a certain amount of (NH
4)
2S
2O
3If reductive agent is less than this ratio, then para benzoquinone does not change into Resorcinol fully.
(4), filter out the concentrated ammonium sulfate fertilizer that obtains of mother liquor of the thick product gained of Resorcinol or pyrocatechol.
Beneficial effect
This patent is raw material with phenol and oxygen, and copper sodium composite salt is catalyzer, and catalyzed oxidation makes benzoquinone and pyrocatechol, the reaction conditions gentleness; Then fractionation by distillation both, the benzoquinone of acquisition reduction obtains the benzoquinone, general scheme is suc as formula (3):
Phenol turnover ratio height is about 94%, transformation efficiency 76 % of Resorcinol, catalyst selectivity height (88.6 %).
Traditional phenol hydroxylation process is successive reaction, be accompanied by the generation of phenol tar, single transformation efficiency low (5 %-15 %), and the productive rate of by product o-phenyl phenol diphenol higher (mass ratio of Pyrogentisinic Acid and o-phenyl phenol is between between the 0.7:1 to 1.5:1), but the phenol conversion that the present invention obtains is 94% for the total conversion rate of Pyrogentisinic Acid's diphenol and pyrocatechol, and the mass ratio of Resorcinol and pyrocatechol is 4.2:1.
Reductive agent is in the steel-making wastewater treatment process, has extracted useful component ammonium thiocyanate residue afterwards, and belonging to turns waste into wealth; The main component of performance reductive agent effect is ammonium thiosulfate in reaction process, and benzoquinones is reduced into Resorcinol; And ammonium thiosulfate is oxidized to the ammonium sulfate as fertilizer sources, a no liquid waste disposal difficult problem; Another raw material oxygen cheaply is easy to get, and uses oxygen in the production, the temperature and pressure gentleness, so production security is good; Entire equipment instead is made up of equipment such as reactor, steam distillation knockout tower, reduction kettle and crystallization kettles successively, a Process of Hydroquinone Production enterprise that produces 2000 tons per year, and gross investment about 1,500 ten thousand yuan (not containing cost of land) therefore, constitutes simple, good in economic efficiency; This method atom economy height, by product is few, and catalyst recirculation is applied mechanically, and contamination-free is discharged.
Description of drawings
Fig. 1 is the benzoquinone's for preparing of the embodiment of the invention 1 infared spectrum.From figure, can draw: 3300 cm
-1Be phenolic hydroxyl group O-H stretching vibration absorption peak, 1580 cm
-1With 1480 cm
-1Be the C=C stretching vibration absorption peak of phenyl ring, 1220 cm
-1It is the C-O stretching vibration absorption peak of phenol.
Embodiment
Further specify concrete technical scheme of the present invention by the following examples.
(1) gets 10 g phenol and the composite salt (CuSO of 5 g copper sodium
4: NaCl=1:3, available from Shanghai chemical reagent work) join in the three-necked bottle that contains 50 mL methyl alcohol, aerating oxygen, 60 ℃ were refluxed 6 hours, and TLC monitors reaction process.
(2) steam methyl alcohol, add 10 mL water in the residuum, steam distillation is colourless to distillate.Concentrate, cooling is filtered, and isolates benzoquinone 8.62 g (productive rate: 75.0 %) in the distillate.The steam distillation mother liquor concentrates, and cooling is filtered, and isolates adjacent benzene diquinone 2.07 g(productive rates: 18.0 %).
(3) get benzoquinone 8.62 g and 9.0 g ammonium thiosulfate/ammonium sulfate mixture (ammonium thiosulfate 68.5wt%, ammonium sulfate 31.5wt%, Nangang's steel-smelting sewerage extracts the residue behind the potassium sulfocyanate) join in the 17 mL hot water, stirred 20 minutes, sulfuric acid adjust pH to 1, the thick product of Resorcinol is separated out in cooling, obtain colourless acicular crystal Resorcinol 7.87 g through ethyl alcohol recrystallization, productive rate: 89.6 %.Be 67.8 % in the phenol overall yield.
(4) adjacent benzene diquinone 2.07 g and ammonium thiosulfate/ammonium sulfate mixture (ammonium thiosulfate of 68.5 quality %) 2.2 g join in the 5 mL hot water, stirred 20 minutes, cooling, sulfuric acid adjust pH to 1, separate out the thick product of pyrocatechol under acid, obtain 1.92 g clear crystal pyrocatechol (productive rates: 91.1 %) through ethyl alcohol recrystallization.In phenol, overall yield: 16.5 %.
(5) will filter mother liquid obtainedly, and concentrate, the control temperature is separated out ammonium sulfate, can make fertilizer and use.
Embodiment 2
(1) gets 50 g phenol and the composite salt (CuSO of 5 g copper sodium
4: NaCl=1:2, CuSO
4With NaCl available from Shanghai chemical reagent work) join in the three-necked bottle that contains 250 mL ethanol, aerating oxygen, 70 ℃ were refluxed 2 hours, TLC monitors reaction process.
(2) steam ethanol, add 50 mL water in the residuum, steam distillation, colourless up to distillate.Concentrate, cooling is filtered, and isolates benzoquinone 43.3 g (productive rate: 75.4%) in the distillate.The steam distillation mother liquor concentrates, and cooling is filtered, and isolates adjacent benzene diquinone 10.2 g(productive rates: 17.8 %).
(3) get benzoquinone 43.3 g and 45.0 g ammonium thiosulfate/ammonium sulfate mixture (ammonium thiosulfate 68.5wt%, ammonium sulfate 31.5wt%, Nangang's steel-smelting sewerage extracts the residue behind the potassium sulfocyanate) join in the 85 mL hot water, stirred 20 minutes, sulfuric acid adjust pH to 1, the thick product of Resorcinol is separated out in cooling, obtain colourless acicular crystal Resorcinol 39.7 g through ethyl alcohol recrystallization, productive rate: 90.1 %.Be 67.9 % in the phenol overall yield.
(4) adjacent benzene diquinone 10.2 g and ammonium thiosulfate/ammonium sulfate mixture (ammonium thiosulfate of 68.5 quality %) 10.6 g join in the 5 mL hot water, stirred 20 minutes, cooling, sulfuric acid adjust pH to 1, separate out the thick product of pyrocatechol under acid, obtain 9.54 g clear crystal pyrocatechol (productive rates: 91.8 %) through ethyl alcohol recrystallization.In phenol, overall yield: 16.3 %.
(5) will filter mother liquid obtainedly, and concentrate, the control temperature is separated out ammonium sulfate, can make fertilizer and use.
Embodiment 3
(1) gets 100 g phenol and the composite salt of 7.5 g copper sodium (Cu (NO
3)
2: NaCl=1:3, Cu (NO
3)
2With NaCl available from Shanghai chemical reagent work) join in the three-necked bottle that contains 500 mL propyl alcohol, the heating (about 70 ℃ of temperature), aerating oxygen, TLC monitors reaction, reacts completely in 2 hours.
(2) steam ethanol, add 100 mL water in the residuum, steam distillation, colourless up to distillate.Concentrate, cooling is filtered, and isolates benzoquinone 87.2 g (productive rate: 75.9 %) in the distillate.The steam distillation mother liquor concentrates, and cooling is filtered, and isolates adjacent benzene diquinone 20.1 g(productive rates: 17.5 %).
(3) get benzoquinone 87.2 g and 90.7 g ammonium thiosulfate/ammonium sulfate mixture (ammonium thiosulfate 68.5wt%, ammonium sulfate 31.5wt%, Nangang's steel-smelting sewerage extracts the residue behind the potassium sulfocyanate) join in the 150 mL hot water, stirred 20 minutes, sulfuric acid adjust pH to 1, the thick product of Resorcinol is separated out in cooling, obtain colourless acicular crystal Resorcinol 79.8 g through ethyl alcohol recrystallization, productive rate: 89.9 %.Be 68.2 % in the phenol overall yield.
(4) adjacent benzene diquinone 20.1 g and 20.9 g ammonium thiosulfate/ammonium sulfate mixture (ammonium thiosulfate 68.5wt%, ammonium sulfate 31.5wt%, Nangang's steel-smelting sewerage extracts the residue behind the potassium sulfocyanate) join in the 50 mL hot water, stirred 20 minutes, cooling, sulfuric acid adjust pH to 1 is separated out the thick product of pyrocatechol under the acidity, obtains 18.8 g clear crystal pyrocatechol (productive rates: 91.9 %) through ethyl alcohol recrystallization.In phenol, overall yield: 16.1 %.
(5) will filter mother liquid obtainedly, and concentrate, the control temperature is separated out ammonium sulfate, can make fertilizer and use.
Embodiment 4
Except the phenol of this place record and the solvent of the composite salt of copper sodium are that all the other contents are all identical with embodiment 1 mixture of methyl alcohol and ethanol (v:v=1:1), in phenol, overall yield: 16.9 %.。
Embodiment 5
Except the phenol of this place record and the solvent of the composite salt of copper sodium are the butanols, all the other contents are all identical with embodiment 1, in phenol, and overall yield: 17.5 %.。
Embodiment 6
Except the phenol of this place record and the solvent of the composite salt of copper sodium be that all the other contents are all identical with embodiment 1 mixture of methyl alcohol and ethanol (v:v=1:1), in phenol, overall yield: 17.6 %.。
Embodiment 7
Except the phenol of this place record and the solvent of the composite salt of copper sodium be that all the other contents are all identical with embodiment 1 mixture of methyl alcohol, ethanol, propyl alcohol (v:v:v=1:2:1), in phenol, overall yield: 16.6%.
Above-mentioned embodiment does not limit technical scheme of the present invention in any form, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops on protection scope of the present invention.
Claims (3)
1. the synthetic method of a Resorcinol is characterized in that may further comprise the steps:
(1) phenol and Oxygen Catalytic Oxidation generate the mixture of benzoquinone and adjacent benzene diquinone, and catalyzer is the composite salt of copper sodium;
(2) steam solvent, add water in the residuum, through fractionation by distillation benzoquinone and adjacent benzene diquinone;
(3) isolated benzoquinone obtains Resorcinol by the reductive agent reduction, filters out the big and heavy crystallization of Resorcinol and obtains the Resorcinol crystal; Described reductive agent is in the steel-making wastewater treatment process, has extracted the residue behind the ammonium thiocyanate, and the main chemical compositions of this residue is (NH
4)
2S
2O
3(NH
4)
2SO
4;Reductive agent and benzoquinone's mass ratio is 1.04:1;
(4) mother liquor that filters out the thick product gained of Resorcinol or pyrocatechol concentrates and to obtain ammonium sulfate fertilizer.
2. the synthetic method of Resorcinol according to claim 1 is characterized in that the mol ratio of the middle catalyzer copper sodium composite salt of step (1) and phenol is between the 1:2 to 1:20, and temperature of reaction is 60-80
oC, reaction pressure is normal pressure, and the reaction times is 2-6 hour, and solvent for use is the mixture of two or three among methyl alcohol, ethanol, propyl alcohol, butanols or the above-mentioned four kinds of alcohol.
3. the synthetic method of Resorcinol according to claim 1, it is characterized in that fractionation by distillation step in the step (2) is that the color of the aqueous solution that goes out according to steam distillation is judged progress, when the aqueous solution that distills out gradually becomes colourless by yellow, stop distillation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9630899B1 (en) | 2015-10-26 | 2017-04-25 | Chang Chun Plastics Co. Ltd. | Process for producing hydroquinone and derivates |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603489B (en) * | 2012-02-09 | 2013-12-18 | 苏州久王多铵盐科技有限公司 | Use method of ammonium thiosulfate byproduct produced in steelmaking wastewater treatment process as reducing agent |
| CN104557470B (en) * | 2015-01-23 | 2016-03-16 | 湖北开元化工科技股份有限公司 | A kind of para benzoquinone is reduced into the method for quinhydrones through the agent of over cure series of reductions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4257968A (en) * | 1979-10-04 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Oxidation of phenol to p-benzoquinone in acetonitrile/methanol cosolvent |
| CN101012065A (en) * | 2007-01-29 | 2007-08-08 | 苏州久王多铵盐科技有限公司 | Method of separating multi-ammonium compound salt |
-
2011
- 2011-11-02 CN CN 201110341287 patent/CN102351656B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4257968A (en) * | 1979-10-04 | 1981-03-24 | E. I. Du Pont De Nemours And Company | Oxidation of phenol to p-benzoquinone in acetonitrile/methanol cosolvent |
| CN101012065A (en) * | 2007-01-29 | 2007-08-08 | 苏州久王多铵盐科技有限公司 | Method of separating multi-ammonium compound salt |
Non-Patent Citations (2)
| Title |
|---|
| 胡玉才等.苯酚催化氧化制对苯二酚的两步法工艺.《化学反应工程与工艺》.2006,第22卷(第6期),544-548. |
| 苯酚催化氧化制对苯二酚的两步法工艺;胡玉才等;《化学反应工程与工艺》;20061231;第22卷(第6期);544-548 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9630899B1 (en) | 2015-10-26 | 2017-04-25 | Chang Chun Plastics Co. Ltd. | Process for producing hydroquinone and derivates |
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